WO2009127009A1 - Polymères de condensation - Google Patents

Polymères de condensation Download PDF

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Publication number
WO2009127009A1
WO2009127009A1 PCT/AU2009/000477 AU2009000477W WO2009127009A1 WO 2009127009 A1 WO2009127009 A1 WO 2009127009A1 AU 2009000477 W AU2009000477 W AU 2009000477W WO 2009127009 A1 WO2009127009 A1 WO 2009127009A1
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WIPO (PCT)
Prior art keywords
acid
hydroxy
poly
cyclic ester
nylon
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PCT/AU2009/000477
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English (en)
Inventor
Florian Hans Maximilian Graichen
Michael Shane O'shea
Gary Peeters
Andrew Charles Warden
Original Assignee
Commonwealth Scientific And Industrial Research Organisation
Grains Research And Development Corporation
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Priority claimed from AU2008901955A external-priority patent/AU2008901955A0/en
Application filed by Commonwealth Scientific And Industrial Research Organisation, Grains Research And Development Corporation filed Critical Commonwealth Scientific And Industrial Research Organisation
Publication of WO2009127009A1 publication Critical patent/WO2009127009A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds

Definitions

  • the present invention relates in general to condensation polymers.
  • the invention relates to aliphatic condensation polymers having modified properties
  • Condensation polymers such as polyesters and polyamides may be prepared with a diverse array of physical and chemical properties.
  • condensation polymers may vary widely in their stiffness, hardness, elasticity, tensile strength, density, and may or may not be susceptible to biodegradation.
  • aliphatic condensation polymers present their own unique physical and chemical properties.
  • aliphatic polyesters are known to exhibit good biodegradability.
  • aliphatic condensation polymers can lack the physical and/or chemical properties required for use in certain applications.
  • polylactic acid has relatively poor flexibility and its use in film based applications (e.g. as a packaging material) is limited.
  • a number of techniques for improving the physical and/or chemical properties of aliphatic condensation polymers have been developed.
  • specialty monomers that can influence the physical and/or chemical properties of the polymer may be used in conjunction with the conventional monomers during the condensation polymerisation manufacturing process.
  • deriving new and improved properties of condensation polymers in this way necessarily requires the use of rather specialised condensation polymerisation equipment.
  • the present invention provides a method of preparing a polymer composition, the method comprising melt mixing an aliphatic condensation polymer with a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an ⁇ -oxy carbonyl moiety of general formula (I):
  • R is an optionally substituted aliphatic hydrocarbon having 3 or more carbon atoms.
  • the resulting modified condensation polymer includes as part its polymeric backbone the ⁇ -oxy carbonyl moiety of a general formula (T).
  • T general formula (T)
  • the presence of the moiety as part of the polymer backbone is believed to impart new and/or improved properties to the modified condensation polymer.
  • the present invention further provides a method for modifying an aliphatic condensation polymer, the method comprising melt mixing the condensation polymer with a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an ce-oxy carbonyl moiety of general formula (I).
  • the methods of the invention can advantageously be performed using conventional melt mixing equipment known in the art.
  • the methods will be performed by introducing the cyclic ester and the condensation polymer individually or collectively into the appropriate melt mixing equipment.
  • the cyclic ester might be introduced to condensation polymer already in a molten state, or a mixture of the cyclic ester and the condensation polymer may be subjected to melt mixing.
  • the cyclic ester might also be provided in the form of a composition such as a masterbatch or concentrate which is subsequently let down into an aliphatic condensation polymer to be modified.
  • the composition will generally comprise the cyclic ester and one or more polymers (commonly referred to as a carrier polymer(s)).
  • the carrier polymer may be the same or different to the condensation polymer that is to be modified.
  • the carrier polymer(s) is an aliphatic condensation polymer.
  • the composition may be a physical blend of the cyclic ester and one or more carrier polymers, and/or may itself be prepared by melt mixing the cyclic ester with one or more carrier polymers.
  • the present invention therefore also provides a composition for modifying an aliphatic condensation polymer, the composition comprising one or more carrier polymers and a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an ⁇ -oxy carbonyl moiety of general formula (I), and/or a product formed by melt mixing a composition comprising one or more carrier polymers and a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an ⁇ -oxy carbonyl moiety of general formula (I).
  • the polymer composition comprises an aliphatic condensation polymer and a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an ⁇ -oxy carbonyl moiety of general formula (I) and/or a product formed by melt mixing a composition comprising an aliphatic condensation polymer and a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an ⁇ -oxy carbonyl moiety of general formula (I).
  • Aliphatic condensation polymers modified in accordance with the invention have been found to exhibit new and/or improved properties such as improved flexibility relative to the condensation polymer prior to being modified.
  • the cyclic esters used in accordance with the invention can advantageously be prepared using hydroxycarboxylic acids, a renewable resource that can be derived from plants and animals.
  • condensation polymer is intended to mean a polymer that has been formed via a condensation or step-wise polymerisation reaction.
  • condensation polymers include polyesters, polyamide and copolymers thereof.
  • the condensation polymers used are polyesters, polyamides, and copolymers thereof.
  • Condensation polymers used in accordance with the invention are "aliphatic condensation polymers".
  • aliphatic condensation polymers is meant that the polymer backbone does not incorporate an aromatic moiety.
  • polyethylene terephthalate i.e. PET
  • PET polyethylene terephthalate
  • polymer backbone is meant the main structure of the polymer on to which substituents may be attached.
  • the main structure of the polymer may be linear or branched.
  • the condensation polymers may also be acyclic (i.e. where the polymer backbone does not incorporate a cyclic moiety). Although the polymer backbone of the aliphatic condensation polymers will not incorporate an aromatic moiety (and possibly not a cyclic moiety), an aromatic or cyclic moiety may nonetheless be present in a position that is pendant from the polymer backbone. However, the aliphatic condensation polymers used in accordance with the invention will not generally comprise a pendant aromatic or cyclic moiety.
  • Aliphatic polyesters that may be used in the invention include homo- and copolymers of ⁇ oly(hydroxyalkanoates) and homo- and copolymers of those aliphatic polyesters derived from the reaction product of one or more alkyldiols with one or more alkyldicarboxylic acids (or acyl derivatives). Miscible and immiscible blends of aliphatic polyesters may also be used.
  • One class of aliphatic polyester includes poly(hydroxyalkanoates) derived by condensation or ring-opening polymerization of hydroxycarboxylic acids, or derivatives thereof.
  • Suitable poly(hydroxyalkanoates) may be represented by the formula H(O — R a — C(O) — ) n OH, where R a is an alkylene moiety that may be linear or branched and n is a number from 1 to 20, preferably 1 to 12.
  • R a may further comprise one or more caternary (i.e. in chain) ether oxygen atoms.
  • the R a group of the hydroxycarboxylic acids is such that the pendant hydroxyl group is a primary or secondary hydroxyl group.
  • Useful poly(hydroxyalkanoates) include, for example, homo- and copolymers of poly(3- hydroxybutyrate), poly(4-hydroxybutyrate), poly(3-hydroxyvalerate), poly(lactic acid) (also known as polylactide), poly(3-hydroxypropanoate), poly(4-hydropcntanoate), ⁇ oly(3- hydroxypentanoate), poly(3-hydroxyhexanoate), poly(3-hydroxyheptanoate), poly(3- hydroxyoctanoate), polydioxanone, and polycaprolactone, polyglycolic acid (also known as polyglycolide).
  • polyglycolic acid also known as polyglycolide
  • Copolymers of two or more of the above hydroxycarboxylic acids may also be used, for example, to provide for poly(3-hydroxybutyrate-co-3-hydroxyvalerate), polyClactate-co-S-hydroxypropanoate) and poly ⁇ lycolide-co-p-dioxanone). Blends of two or more of the poly(hydroxyalkanoates) may also be used.
  • a further class of aliphatic polyester includes those aliphatic polyesters derived from the reaction product of one or more alkyldiols with one or more alkyldicarboxylic acids (or acyl derivatives). Such polyesters may have the general formula (II):
  • R b and R c each independently represent an alkylene moiety that may be linear or branched having from 1 to 20, preferably 1 to 12 carbon atoms, and p is a number such that the ester is polymeric, and is preferably a number such that the molecular weight of the aliphatic polyester is 10,000 to 300,000, more preferably from about 30,000 to 200,000.
  • Each m and n is independently 0 or 1.
  • R b and R c may further comprise one or more caternary (i.e. in chain) ether oxygen atoms.
  • aliphatic polyesters include those homo- and copolymers derived from (a) one or more of the following diacids (or derivative thereof): succinic acid, adipic acid, 1,12 dicarboxydodecane, fumaric acid, and maleic acid and (b) one of more of the following diols: ethylene glycol, polyethylene glycol, 1,2-propane diol, 1,3-propanediol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and polypropylene glycol, and (c) optionally a small amount, e.g. 0.5-7.0 mole % of a polyol with a functionality greater than two such as glycerol, or pentaerythritol.
  • diacids or derivative thereof
  • succinic acid succin
  • Such aliphatic polyesters may include polybutylenesuccinate homopolymer, polybutylene adipate homopolmer, polybutyleneadipate-succinate copolymer, polyethylenesuccinate- adipate copolymer, polyethylene adipate homopolymer.
  • Common commercially available aliphatic polyesters include polylactide, polyglycolide, polylactide-co-glycolide, poly(L-lactide-co-trimethylene carbonate), poly(dioxanone), poly(butylene succinate), and poly(butylene adipate).
  • Blends of two or more aliphatic polyesters may also be used in accordance with the invention.
  • Aliphatic polyamides that may be used in the invention include those characterised by the presence of recurring carbonamide groups that form part of the polymer backbone and which are separated from one another by at least two aliphatic carbon atoms. Suitable aliphatic polyamides therefore include those having recurring units represented by general formulae (III) or (IV):
  • R d and R e are the same or different and are each independently alkylene groups of at least two carbon atoms, for example alkylene having about two to about 20 carbon atoms, preferably alkylene having about two to about 12 carbon atoms.
  • poly(tetramethylene adipamide) (nylon 4,6); pory(hexamethylene adipamide) (nylon 6,6); poly(hexamethylene azelamide) (nylon 6,9); poly(hexamethylene sebacamide) (nylon 6,10); poly(heptamethylene pimelamide) (nylon 7,7); poly(octamethylene suberamide) (nylon 8,8); pory(nonamethylene azelamide) (nylon 9,9); poly(decamethylene azelamide) (nylon 10,9); and the like.
  • polyamides are also those formed by polymerization of alkyl amino acids and derivatives thereof (e.g. lactams) and include poly(4-aminobutyric acid) (nylon 4); poly(6- aminohexanoic acid) (nylon 6); poly(7-amino-heptanoic acid) (nylon 7); poly(8- aminoocatanoic acid) (nylon 8); poly(9-aminononanoic acid) (nylon 9); poly(10- aminodecanoic acid) (nylon 10); poly(ll-aminoundecanoic acid) (nylon 11); poly(12- aminododecanoic acid) (nylon 12); and the like.
  • Blends of two or more aliphatic polyamides may also be used in accordance with the invention.
  • cyclic ester is intended to mean a cyclic molecule having at least one ring (or cycle) within its molecular structure that contains an ester moiety that forms part of that cycle.
  • the cyclic ester has at least two ester moieties that form part of its cycle.
  • cyclic esters are commonly referred to as macrocyclic oligoesters.
  • cyclic esters used in accordance with the invention comprise as part of their cycle an ⁇ -oxy carbonyl moiety of general formula (I):
  • R is an optionally substituted aliphatic hydrocarbon having three or more carbon atoms.
  • R in general formula (I) is an optionally substituted aliphatic hydrocarbon having three or more carbon atoms.
  • aliphatic hydrocarbon is meant a non-aromatic hydrocarbon.
  • the hydrocarbon group R may also be an acyclic hydrocarbon (i.e. a non-cyclic hydrocarbon).
  • the hydrocarbon group R may be a linear or branched alkyl, alkenyl, or alkynyl group.
  • the hydrocarbon group R may be saturated or unsaturated. Where the hydrocarbon group R is unsaturated, it may be mono- or poly-unsaturated, and include both cis- and trans- isomers.
  • the hydrocarbon R will generally have 3 to 40 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 6 to 20 carbon atoms.
  • the hydrocarbon R may be substituted, for example with a hetero atom containing moiety and/or an aromatic or cyclic moiety. In some embodiments the R group is not substituted.
  • the modified condensation polymers in accordance with the invention can advantageously undergo reaction through the reactive functional groups within or substituted on the hydrocarbon R.
  • the hydrocarbon group R is unsaturated
  • the unsaturated bonds may take part in crosslinking reactions (i.e. oxidative crosslinking similar to that which occurs in alkyd paints, or free radical mediated reactions), and free radical mediated grafting reactions.
  • Crosslinking and grafting reactions may also be conducted through reactive functional group substituents on the hydrocarbon group R.
  • Providing the hydrocarbon group R with one or more reactive functional groups can advantageously enable organic or inorganic moieties to be tethered to the polymer backbone through reaction of the moieties with such groups.
  • the organic or inorganic moieties may be conveniently tethered to the R group of the cyclic ester prior to it being melt mixed with the aliphatic condensation polymer, or tethered to the R group after the cyclic ester has been melt mixed with the aliphatic condensation polymer.
  • the R group of general formula (I) is an aliphatic hydrocarbon comprising conjugated double and/or triple bonds.
  • conjugation is in the form of an yne-yne, ene-ene, yne-yne-yne, yne-yne-ene-, ene-yne-yne or yne-ene-yne moiety.
  • alkyl used either alone or in compound words denotes straight chain, branched or cyclic alkyl, for example C 1-40 alkyl, or C 1-20 or C 1-10 .
  • straight chain and branched alkyl include methyl, ethyl, ⁇ -propyl, isopropyl, ra-butyl, sec- butyl, t-butyl, n-pentyl, 1,2-dimethylpropyl, 1,1-dimethyl-propyl, hexyl, 4-methylpentyl, 1- methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3- dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1,2- trimethylpropyl, heptyl, 5-methylhexyl, 1-methylhexyl, 1-methylhexy
  • cyclic alkyl examples include mono- or polycyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like. Where an alkyl group is referred to generally as "propyl", butyl” etc, it will be understood that this can refer to any of straight, branched and cyclic isomers where appropriate. An alkyl group may be optionally substituted by one or more optional substituents as herein defined.
  • alkenyl denotes groups formed from straight chain, branched or cyclic hydrocarbon residues containing at least one carbon to carbon double bond including ethylenically mono-, di- or polyunsaturated alkyl or cycloalkyl groups as previously defined, for example C 2-40 alkenyl, or C 2-20 or C 2-10 .
  • alkenyl is intended to include propenyl, butylenyl, pentenyl, hexaenyl, heptaenyl, octaenyl, nonaenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nondecenyl, eicosenyl hydrocarbon groups with one or more carbon to carbon double bonds.
  • alkenyl examples include vinyl, allyl, 1-methylvinyl, butenyl, iso-butenyl, 3-methyl-2-butenyl, 1 -pentenyl, cyclopentenyl, 1-methyl- cyclopentenyl, 1-hexenyl, 3-hexenyl, cyclohexenyl, 1-heptenyl, 3-heptenyl, 1-octenyl, cyclooctenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 3-decenyl, 1,3-butadienyl, 1,4- pentadienyl, 1,3-cyclopentadienyl, 1,3-hexadienyl, 1,4-hexadienyl, 1,3-cyclohexadienyl, 1,4-cyclohexadienyl, 1,3-cycloheptadienyl, 1,3,5-cycloh
  • alkynyl denotes groups formed from straight chain, branched or cyclic hydrocarbon residues containing at least one carbon-carbon triple bond including ethylenically mono-, di- or polyunsaturated alkyl or cycloalkyl groups as previously defined, for example, C 2-40 alkenyl, or C 2-20 or C 2-10 .
  • alkynyl is intended to include propynyl, butylynyl, pentynyl, hexaynyl, heptaynyl, octaynyl, nonaynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nondecynyl, eicosynyl hydrocarbon groups with one or more carbon to carbon triple bonds.
  • alkynyl examples include ethynyl, 1 -propynyl, 2-propynyl, and butynyl isomers, and pentynyl isomers.
  • An alkynyl group may be optionally substituted by one or more optional substituents as herein defined.
  • An alkenyl group may comprise a carbon to carbon triple bond and an alkynyl group may comprise a carbon to carbon double bond (i.e. so called ene-yne or yne-ene groups).
  • aryl denotes any of single, polynuclear, conjugated and fused residues of aromatic hydrocarbon ring systems.
  • aryl include phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, tetrahydronaphthyl, anthracenyl, dihydroanthracenyl, benzanthracenyl, dibenzanthracenyl, phenanthrenyl, fluorenyl, pyrenyl, idenyl, azulenyl, chrysenyl.
  • Preferred aryl include phenyl and naphthyl.
  • An aryl group may be optionally substituted by one or more optional substituents as herein defined.
  • alkylene As used herein, the terms “alkylene”, “alkenylene”, and “arylene” are intended to denote the divalent forms of “alkyl”, “alkenyl”, and “aryl”, respectively, as herein defined.
  • optionally substituted is taken to mean that a group may or may not be substituted or fused (so as to form a condensed polycyclic group) with one, two, three or more of organic and inorganic groups (i.e. the optional substituent) including those selected from: alkyl, alkenyl, alkynyl, carbocyclyl, aryl, heterocyclyl, heteroaryl, acyl, aralkyl, alkaryl, alkheterocyclyl, alkheteroaryl, alkcarbocyclyl, halo, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, halocarbocyclyl, haloheterocyclyl, haloheteroaryl, haloacyl, haloaryalkyl, hydroxy, hydroxyalkyl, hydroxyalkenyl, hydroxyalkynyl, hydroxycarbocyclyl, hydroxy
  • a group is optionally substituted with a reactive functional group or moiety.
  • reactive functional groups or moieties include epoxy, anhydride, cyclic ester (e.g. lactone or higher cyclic oligoester), cyclic amide (e.g. lactam or higher cyclic oligoamide), oxazoline and carbodimide.
  • a group is optionally substituted with a polymer chain.
  • An example of such a polymer chain includes a polyether chain.
  • Preferred optional substituents include the aforementioned reactive functional groups or moieties, polymer chains and alkyl, (e.g. C 1-6 alkyl such as methyl, ethyl, propyl, butyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl), hydroxyalkyl (e.g. hydroxymethyl, hydroxyethyl, hydroxypropyl), alkoxyalkyl (e.g.
  • alkoxy e.g. C 1-6 alkoxy such as methoxy, ethoxy, propoxy, butoxy, cyclopropoxy, cyclobutoxy
  • halo trifluoromethyl, trichloromethyl, tribromomethyl, hydroxy, phenyl (which itself may be further substituted e.g., by C 1-6 alkyl, halo, hydroxy, hydroxyC 1-6 alkyl, C 1-6 alkoxy, haloC 1-6 alkyl, cyano, nitro OC(O)C 1-6 alkyl, and amino)
  • benzyl wherein benzyl itself may be further substituted e.g., by C 1-6 alkyl, halo, hydroxy, hydroxyC 1-6 alkyl, C 1-6 alkoxy, haloC 1-6 alkyl etc) alkoxy (e.g. C 1-6 alkoxy such as methoxy, ethoxy, propoxy, butoxy, cyclopropoxy, cycl
  • C 1-6 alkyl such as methylamino, ethylamino, propylamino etc
  • dialkylamino e.g. C 1-6 alkyl, such as dimethylaniino, diethylamino, dipropylamino
  • acylamino e.g.
  • phenylamino (wherein phenyl itself may be further substituted e.g., by C 1-6 alkyl, halo, hydroxy hydroxyC 1-6 alkyl, C 1-6 alkoxy, haloC 1-6 alkyl, cyano, nitro OC(O)C 1-6 alkyl, and amino), nitro, formyl, -C(O)-alkyl (e.g. C 1-6 alkyl, such as acetyl), O-C(O)-alkyl (e.g.
  • C 1- 6 alkyl such as acetyloxy
  • benzoyl wherein the phenyl group itself may be further substituted e.g., by C 1-6 alkyl, halo, hydroxy hydroxyC 1-6 alkyl, C 1-6 alkoxy, haloC 1-6 alkyl, cyano, nitro OC(O)C 1-6 alkyl, and amino
  • C 1-6 alkyl such as methyl ester, ethyl ester, propyl ester, butyl ester
  • C0 2 phenyl wherein phenyl itself may be further substituted e.g., by C 1-6 alkyl, halo, hydroxy, hydroxyl C 1-6 alkyl, C 1-6 alkoxy, halo C 1-6 alkyl, cyano, nitro OC(O)C 1-6 alkyl, and amino
  • CONH 2 CONHphenyl (wherein phenyl itself may be further substituted e.g., by C 1-6 alkyl, halo, hydroxy, hydroxyl C 1-6 alkyl, C 1-6 alkoxy, halo C 1-6 alkyl, cyano, nitro OC(O)C 1-6 alkyl, and amino)
  • CONHbenzyl wherein benzyl itself may be further substituted e.g., by C 1-6 alkyl, halo, hydroxy hydroxy
  • C 1-6 alkyl such as methyl ester, ethyl ester, propyl ester, butyl amide) CONHdialkyl (e.g. C 1-6 alkyl) aminoalkyl (e.g., HN C 1-6 alkyl-, C 1-6 alkylHN-C 1-6 alkyl- and (C 1-6 alkyl) 2 N-C 1-6 alkyl-), thioalkyl (e.g., HS C 1-6 alkyl-), carboxyalkyl (e.g., HO 2 CC 1-6 alkyl-), carboxyesteralkyl (e.g., C 1-6 alkylO 2 CC 1-6 alkyl-), amidoalkyl (e.g., H 2 N(O)CC 1-6 alkyl-, H(C 1-6 alkyl)N(O)CC 1-6 alkyl-), formylalkyl (e.g., OHCC 1-6 alkyl-), acylalkyl
  • the aliphatic hydrocarbon group R is optionally substituted with a cyclic ester, cyclic amide, or polyether chain.
  • halogen denotes fluorine, chlorine, bromine or iodine (fluoro, chloro, bromo or iodo). Preferred halogens are chlorine, bromine or iodine.
  • carbocyclyl includes any of non-aromatic monocyclic, polycyclic, fused or conjugated hydrocarbon residues, preferably C 3-20 (e.g. C 3-1O or C 3-8 ).
  • the rings may be saturated, e.g. cycloalkyl, or may possess one or more double bonds (cycloalkenyl) and/or one or more triple bonds (cycloalkynyl).
  • Particularly preferred carbocyclyl moieties are 5-6-membered or 9-10 membered ring systems.
  • Suitable examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, cyclopentadienyl, cyclohexadienyl, cyclooctatetraenyl, indanyl, decalinyl and indenyl.
  • heterocyclyl when used alone or in compound words includes any of monocyclic, polycyclic, fused or conjugated hydrocarbon residues, preferably C 3-20 (e.g. C 3-10 or C 3-8 ) wherein one or more carbon atoms are replaced by a heteroatom so as to provide a non-aromatic residue.
  • Suitable heteroatoms include O, N, S, P and Se, particularly O, N and S. Where two or more carbon atoms are replaced, this may be by two or more of the same heteroatom or by different heteroatoms.
  • the heterocyclyl group may be saturated or partially unsaturated, i.e. possess one or more double bonds. Particularly preferred heterocyclyl are 5-6 and 9-10 membered heterocyclyl.
  • heterocyclyl groups may include azridinyl, oxiranyl, thiiranyl, azetidinyl, oxetanyl, thietanyl, 2H-pyrrolyl, pyrrolidinyl, pyrrolinyl, piperidyl, piperazinyl, morpliolinyl, indolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, thiomorpholinyl, dioxanyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydropyrrolyl, tetrahydrothiophenyl, pyrazolinyl, dioxalanyl, thiazolidinyl, isoxazolidinyl, dihydropyranyl, oxazinyl, thiazinyl, thiomorpholinyl, oxathianyl, dithi
  • heteroaryl includes any of monocyclic, polycyclic, fused or conjugated hydrocarbon residues, wherein one or more carbon atoms are replaced by a heteroatom so as to provide an aromatic residue.
  • Preferred heteroaryl have 3-20 ring atoms, e.g. 3-10.
  • Particularly preferred heteroaryl are 5-6 and 9-10 membered bicyclic ring systems.
  • Suitable heteroatoms include, O, N, S, P and Se, particularly O, N and S. Where two or more carbon atoms are replaced, this may be by two or more of the same heteroatom or by different heteroatoms.
  • heteroaryl groups may include pyridyl, pyrrolyl, thienyl, imidazolyl, furanyl, benzothienyl, isobenzothienyl, benzofuranyl, isobenzofuranyl, indolyl, isoindolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, quinolyl, isoquinolyl, phthalazinyl, 1,5-naphthyridinyl, quinozalinyl, quinazolinyl, quinolinyl, oxazolyl, thiazolyl, isothiazolyl, isoxazolyl, triazolyl, oxadialzolyl, oxatriazolyl, triazinyl, and furazanyl.
  • Preferred acyl includes C(O)-R X , wherein R x is hydrogen or an alkyl, alkenyl, alkynyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl residue.
  • R x is hydrogen or an alkyl, alkenyl, alkynyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl residue.
  • Examples of acyl include formyl, straight chain or branched alkanoyl (e.g.
  • C 1-20 such as, acetyl, propanoyl, butanoyl, 2-methylpropanoyl, pentanoyl, 2,2- dimethylpropanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, nonadecanoyl and icosanoyl; cycloalkylcarbonyl such as cyclopropylcarbonyl cyclobutylcarbonyl, cyclopentylcarbonyl and cyclohexylcarbonyl; aroyl such as benzoyl, toluoyl and naphthoyl; aralkanoyl
  • phenylacetyl phenylpropanoyl, phenylbutanoyl, phenylisobutylyl, phenylpentanoyl and phenylhexanoyl
  • naphthylalkanoyl e.g. naphthylacetyl, naphthylpropanoyl and naplithylbutanoyl
  • aralkenoyl such as phenylalkenoyl (e.g.
  • phenylpropenoyl e.g., phenylbutenoyl, phenylmethacryloyl, phenylpentenoyl and phenylhexenoyl and naphthylalkenoyl (e.g.
  • aryloxyalkanoyl such as phenoxyacetyl and phenoxypropionyl
  • arylthiocarbamoyl such as phenylthiocarbamoyl
  • arylglyoxyloyl such as phenylglyoxyloyl and naphthylglyoxyloyl
  • arylsulfonyl such as phenylsulfonyl and napthylsulfonyl
  • heterocycliccarbonyl heterocyclicalkanoyl such as thienylacetyl, thienylpropanoyl, thienylbutanoyl, thienylpentanoyl, thienylhexanoyl, thiazolylacetyl, thiadiazolylacetyl and tetrazolylacetyl
  • sulfoxide refers to a group -S(O)R y wherein R y is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl, and aralkyl. Examples of preferred R y include C 1-20 alkyl, phenyl and benzyl.
  • sulfonyl refers to a group S(O) 2 -R y , wherein R y is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl and aralkyl.
  • R y is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl and aralkyl.
  • R y is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl and aralkyl.
  • R y is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl and aralkyl.
  • R y include Ci -2 oalkyl, phenyl and benzyl.
  • sulfonamide refers to a group S(O)NR y R y wherein each R y is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl, and aralkyl.
  • R y is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl, and aralkyl.
  • R y include C 1- 20 alkyl, phenyl and benzyl.
  • at least one R y is hydrogen.
  • both R y are hydrogen.
  • amino is used here in its broadest sense as understood in the art and includes groups of the formula NR R wherein R A and R B may be any independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, carbocyclyl, heteroaryl, heterocyclyl, aralkyl, and acyl. R A and R B , together with the nitrogen to which they are attached, may also form a monocyclic, or polycyclic ring system e.g. a 3-10 membered ring, particularly, 5-6 and 9- 10 membered systems. Examples of “amino” include NH 2 , NHalkyl (e.g. C 1-2 oalkyl), NHaryl (e.g.
  • NHaralkyl e.g. NHbenzyl
  • NHacyl e.g. NHC(O)C 1-20 alkyl, NHC(O)phenyl
  • Nalkylalkyl wherein each alkyl, for example C 1-20 , may be the same or different
  • 5 or 6 membered rings optionally containing one or more same or different heteroatoms (e.g. O, N and S).
  • amido examples include C(O)NH 2 , C(O)NHalkyl (e.g. C 1-2O alkyl), C(O)NHaryl (e.g.
  • C(O)NHphenyl C(O)NHaralkyl (e.g. C(O)NHbenzyl), C(O)NHacyl (e.g.
  • carboxy ester is used here in its broadest sense as understood in the art and includes groups having the formula CO 2 R 2 , wherein R z may be selected from groups including alkyl, alkenyl, alkynyl, aryl, carbocyclyl, heteroaryl, heterocyclyl, aralkyl, and acyl.
  • R z may be selected from groups including alkyl, alkenyl, alkynyl, aryl, carbocyclyl, heteroaryl, heterocyclyl, aralkyl, and acyl.
  • Examples of carboxy ester include CO 2 C 1-20 alkyl, CO 2 aryl (e.g.. CO 2 phenyl), CO 2 aralkyl (e.g. CO 2 benzyl).
  • heteroatom refers to any atom other than a carbon atom which may be a member of a cyclic organic group.
  • heteroatoms include nitrogen, oxygen, sulfur, phosphorous, boron, silicon, selenium and tellurium, more particularly nitrogen, oxygen and sulfur.
  • the cyclic ester used in accordance with the invention has at least two ester moieties that form part of its cycle.
  • the carbonyl group of the ⁇ -oxy carbonyl moiety of general formula (I) will in effect provide for one of these ester moieties, and the at least one other ester moiety will be provided by at least one other condensed moiety of a hydroxycarboxylic acid.
  • This at least one further condensed hydroxycarboxylic acid residue may be the same or different to the ⁇ -oxy carbonyl moiety of general formula (I), and will complete the cycle of the cyclic ester as represented by the dashed lines in general formula (I).
  • a cyclic ester suitable for use in accordance with the invention might have a cyclic structure that is formed from the condensed moieties of at least two ⁇ -hydroxycarboxylic acids of general formula (V), or one or more ⁇ -hydroxycarboxylic acids of general formula (V) and one or more other hydroxycarboxylic acids.
  • the general structure of a cyclic ester of this type may be conveniently represented by general formula (VI): An 1 -Bn 2 -An" -Bn 4 An M — Bn 1 (VI)
  • A is a condensation residue of an ce-hydroxycarboxylic acid of general structure (V)
  • B is the condensation residue of a hydroxycarboxylic acid
  • each A and each B may be the same or different
  • each n may be 0 or a positive integer
  • i is a positive integer of the series 1, 2, 3, i, wherein n 1 >1 and n*+n 2 >2.
  • the cyclic ester of general formula (VI) can therefore be seen to represent a macrocyclic oligoester.
  • cyclic ester of general formula (VI) serves merely to illustrate the variety of cyclic structures that may be formed in the preparation of cyclic esters.
  • the cycle size of a cyclic ester may vary depending upon how the cyclic ester is made and from what hydroxycarboxylic acid it is made from.
  • a cyclic ester might also comprise a mixture of different cycle compositions and cycle sizes.
  • the cyclic esters used in accordance with the invention require at least two ester moieties that form part of its cycle.
  • the ester moieties will generally be joined with in the cycle by one or more carbon atoms.
  • the number of ester moieties that may form part of the cycle there will generally be no more than about six of such moieties.
  • the cyclic ester might be a dilactone, trilactone, tetralactone, pentalactone, hexalactone, or mixture thereof.
  • cyclic ester In view of the complexities associated with defining the specific composition of a cyclic ester, it can often be more convenient to refer to the cyclic ester in terms of it being formed from the condensed residue(s) of a particular hydroxycarboxylic acid(s).
  • the cyclic ester used in accordance with the invention comprises as part of its cycle the condensed residue of at least one a- hydroxycarboxylic acid of general formula (V).
  • the cyclic ester used in accordance with the invention comprises as part of its cycle the condensed residue of at least one a- hydroxycarboxylic acid of general formula (V) and at least one other hydroxycarboxylic acid.
  • the cyclic ester used in accordance with the invention comprises as part of its cycle the condensed residue of at least one a- hydroxycarboxylic acid of general formula (V) and at least one ce-hydroxycarboxylic acid of general formula (VII):
  • R 1 is an optionally substituted aliphatic hydrocarbon.
  • fatty acids of general formula (V) will generally undergo condensation reactions with itself or other hydroxycarboxylic acids to at least form a dilactone.
  • the cyclic ester comprises a dilactone formed through the condensation of an ce-hydroxycarboxylic acid of a general formula (V).
  • the cyclic ester comprises a dilactone formed through the condensation of an ⁇ -hydroxycarboxylic acid of general formula (V) and another hydroxycarboxylic acid.
  • the cyclic ester comprises a dilactone formed through the condensation of an ⁇ -hydroxycarboxylic acid of general formula (V) and an a- hydroxycarboxylic acid of general formula (VII).
  • the cyclic ester used in accordance with the invention comprises a dilactone of general formula (VIII):
  • R and R are the same or different and are as hereinbefore defined.
  • R 1 will generally be an aliphatic hydrocarbon having
  • R 1 may be linear or branched, saturated or unsaturated. Where the hydrocarbon is unsaturated, it may be mono- or poly-unsaturated, and includes both cis- and trans-isomers.
  • the hydrocarbon group R 1 may be a linear or branched alkyl, alkenyl, or alkynyl group.
  • R 1 may also be an acyclic hydrocarbon (i.e. a non-cyclic hydrocarbon). Accordingly, R 1 may be the same or different from R.
  • the hydrocarbon R 1 may be substituted, for example with a hetero atom containing moiety and/or an aromatic or cyclic moiety. In some embodiments the R 1 group is not substituted.
  • Cyclic esters suitable for use in accordance with the invention can advantageously be prepared in a similar manner.
  • cyclic esters can be prepared by subjecting an ce-hydroxycarboxylic acid of general formula (V), optionally together with one or more different hydroxycarboxylic acids, to heat under vacuum, or by using several methods described in the literature. (Journal of Biomedical Materials Research Part A, Volume 80A, Issue 1, pp 55-65, Polymer Preprints 2005, 46 (2), 1040, Polymer Preprints 2005 (46 (2), 1006).
  • Cyclic esters suitable for use in accordance with the invention may be conveniently prepared using a variety of ⁇ -hydroxycarboxylic fatty acids of general formula (V).
  • ⁇ -hydroxycarboxylic acids of general formula (V) include ⁇ -hydroxy valeric acid, ⁇ -hydroxy caproic acid, ⁇ -hydroxy caprylic acid, ⁇ -hydroxy pelargonic acid, ⁇ - hydroxy capric acid, ⁇ -hydroxy lauric acid, ⁇ -hydroxy mytistic acid, ⁇ -hydroxy palmitic acid, ⁇ -hydroxy margaric acid, ⁇ -hydroxy stearic acid, ⁇ -hydroxy arachidic acid, ⁇ - hydroxy behenic acid, ⁇ -hydroxy lignoceric acid, ⁇ -hydroxy cerotic acid, ⁇ -hydroxy carboceric acid, ⁇ -hydroxy montanic acid, ⁇ -hydroxy melissic acid, ⁇ -hydroxy lacceroic acid, ⁇ -hydroxy ceromelissic acid, ⁇ -hydroxy geddic acid, ⁇ -hydroxy
  • melt mixing can be performed using methods well known in the art.
  • melt mixing may be achieved using continuous extrusion equipment such as twin screw extruders, single screw extruders, other multiple screw extruders and Farell mixers.
  • Semi-continuous or batch processing equipment may also be used to achieve melt mixing. Examples of such equipment include injection moulders, Banbury mixers and batch mixers. Static melt mixing equipment may also be used.
  • the polymer composition resulting from the melt mixing process will therefore comprise modified aliphatic condensation polymer having the ⁇ -oxy moiety of general fo ⁇ iiula (I) incorporated as part of its polymeric backbone.
  • the polymer composition may also comprise a proportion of cyclic ester that has not undergone reaction with the aliphatic condensation polymer and/or polymer that has formed through ring opening polymerisation of the cyclic ester.
  • ⁇ -oxy moiety of general formula (I) being "incorporated" as part of the polymeric backbone of the aliphatic condensation polymer is meant that the cyclic ester ring opens and becomes covalently bound to the polymeric backbone.
  • this process at least involves the ring opened residue being covalently bound to a terminal end of the polymeric backbone, possibly followed by inter and/or intra polymer chain rearrangement of the ring opened residue such that it becomes located at a non-terminal position within the polymeric backbone (e.g. through a transesterification process).
  • the ring opened form of the cyclic ester may initially attach to a terminal section of the aliphatic condensation polymer, it may nevertheless rearrange its position within the polymer backbone through a transesterification process.
  • an aliphatic condensation polymer modified in accordance with the invention using a cyclic ester of general formula (VIII) may comprise within its polymeric backbone the ring opened residue of the cyclic ester as illustrated below in Scheme 1.
  • the modified condensation polymer will of course generally comprise within its polymeric backbone a number of such ring opened residues.
  • Scheme 1 An illustration of an aliphatic condensation polymer modified in accordance with the invention using a cyclic ester of general formula (VIII), where A and B represent the remainder of the condensation polymer.
  • VIII cyclic ester of general formula (VIII)
  • a and B represent the remainder of the condensation polymer.
  • the R group of the ⁇ -oxy carbonyl moiety of general formula (I) is believed to modify the properties of the condensation polymer.
  • polylactic acid modified in accordance with the invention has been shown to exhibit improved flexibility.
  • Other pendant moieties derived from the cyclic ester, such as R 1 shown above in Scheme 1, may also modify the properties of the condensation polymer.
  • a condensation catalyst may also be employed in order to enhance the melt reaction between the aliphatic condensation polymer and the cyclic ester.
  • Typical condensation catalysts include Lewis acids such as antimony trioxide, titanium oxide and dibutyl tindilaurate.
  • Melt mixing of the aliphatic condensation polymer and the cyclic ester may also be conducted in the presence of one or more additives such as fillers, pigments, stabilisers, blowing agents, nucleating agents, and chain coupling and/or branching agents.
  • additives such as fillers, pigments, stabilisers, blowing agents, nucleating agents, and chain coupling and/or branching agents.
  • Chain coupling and/or branching agents may be used in accordance with the invention to promote an increase in the molecular weight of and/or chain branching in the aliphatic condensation polymer.
  • Such agents include polyfunctional acid anhydrides, epoxy compounds, oxazoline derivatives, oxazolinone derivatives, lactams and related species.
  • Suitable chain coupling and/or branching agents include one or more of the following:
  • Polyepoxides such as bis(3,4-epoxycyclohexylmethyl) adipate; N,N-diglycidyl benzamide (and related diepoxies); N,N-diglycidyl aniline and derivatives; N,N-diglycidylhydantoin, uracil, barbituric acid or isocyamiric acid derivatives; N,N-diglycidyl diimides; N,N- diglycidyl imidazolones; epoxy novolaks; phenyl glycidyl ether; diethyleneglycol diglycidyl ether; Epikote 815 (diglycidyl ether of bisphenol A-epichlorohydrin oligomer).
  • Polyoxazolines/Polyoxazolones such as 2,2-bis(2-oxazoline); 1,3-phenylene bis(2- oxazoline-2), l,2-bis(2-oxazolinyl-2)ethane; 2-phenyl-l,3-oxazoline; 2,2'-bis(5,6-dihydro- 4H-l,3-oxazoline); N,N'-hexamethylenebis (carbamoyl-2-oxazoline; bis[5(4H)- oxazolone); bis(4H-3,lbenzoxazin-4-one); 2,2'-bis(H-3,l-benzozin-4-one).
  • Polyfunctional acid anhydrides such as pyromellitic dianhydride, benzophenonetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic dianhydride, diphenyl sulphone tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3- methyl-3-cyclohexene-l ,2-dicarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)thioether dianhydride, bisphenol-A bisether dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,3,6,7- naphthalenetetracarboxylic acid dianhydride, bis(3,4-dicarboxyphenyl)sulphone dianhydride, 1,2,5,6-naphthal
  • Suitable polyfunctional acid anhydrides include pyromellitic dianhydride, ⁇ , 2,3, A- cyclopentanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and tetrahydrofuran-2,3,4,5-tetracarboxylic acid dianhydride. Most preferably the polyfunctional acid anhydride is pyromellitic dianhydride.
  • Polyacyllactams such as N,N'-terephthaloylbis(caprolactarn) and N,N'- terephthaloylbis(laurolactam) may also be employed.
  • the polymer composition resulting from the methods of the invention may also be subjected to a subsequent solid state condensation polymerisation process. This further processing step can assist with building the molecular weight of the modified aliphatic condensation polymer and can advantageously be conducted using conventional solid state condensation polymerisation techniques and equipment.
  • the cyclic ester When performing the methods of the invention, it may be convenient to provide the cyclic ester, optionally together with any other additives that are to be used, in the form of a composition that can be used for producing the modified aliphatic condensation polymer.
  • This composition may be provided in the form of a physical blend of the respective components and/or in the form a melt mixed product.
  • the invention therefore also provides a composition for modifying an aliphatic condensation polymer, the composition comprising one or more carrier polymers and a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an ⁇ -oxy carbonyl moiety of general formula (I), and/or a product formed by melt mixing a composition comprising one or more carrier polymers and a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an ⁇ -oxy carbonyl moiety of general formula (I).
  • the carrier polymer may in fact be the aliphatic condensation polymer that is to be modified in accordance with the invention.
  • the composition may simplistically be a physical blend of the cyclic ester and the polymer, and the method of the invention is preformed by melt mixing that composition.
  • cyclic ester in the form of a masterbatch or concentrate which can be subsequently melt mixed with an aliphatic condensation polymer that is to be modified in accordance with the invention.
  • masterbatch or “concentrate” (to be used synonymously herein) has the common meaning as would be understood by one skilled in the art. With particular reference to the present invention, these terms are therefore intended to mean a composition comprising the cyclic ester and one or more carrier polymers, which composition is to be subsequently let down in an aliphatic condensation polymer in order to perform the methods of the invention.
  • the masterbatch may be formed by melt mixing the cyclic ester with a carrier polymer that is considered appropriate under the circumstance to be melt mixed with the aliphatic condensation polymer that is to be modified.
  • the carrier polymer may be an aliphatic condensation polymer, for example an aliphatic condensation polymer of the same type as the one that is to be modified.
  • the carrier polymer is an aliphatic condensation polymer
  • the process of making the masterbatch in effect employs the method of the invention.
  • the intention is for the masterbatch to be employed in performing the methods of the invention, hi other words, it is the intention that the masterbatch will comprise unreacted cyclic ester that can be subsequently melt mixed with an aliphatic condensation polymer so as to perform the methods of the invention.
  • a masterbatch formed by melt mixing the cyclic ester with an aliphatic condensation polymer may itself comprise aliphatic condensation polymer that has been modified in accordance with the invention. Melt mixing this modified aliphatic condensation polymer per se with further aliphatic condensation polymer (as will be the case when the masterbatch is melt mixed with an aliphatic condensation polymer) can itself result in the further aliphatic condensation polymer being modified as described herein (e.g. in the case of polyesters, through transesterification reactions).
  • Aliphatic condensation polymers that may be used as a carrier polymer in the compositions of the invention include those described herein.
  • Preparing a masterbatch by melt mixing the cyclic ester with an aliphatic condensation polymer and then subsequently melt mixing the masterbatch with an aliphatic condensation polymer is believed to provide a more efficient and effective means of incorporating the ring opended residues as part of the polymeric backbone of the aliphatic condensation polymer.
  • melt mixing of the cyclic ester and the aliphatic condensation polymers will be conducted at a temperature ranging from about 120°C to about 240°C.
  • the properties of the aliphatic condensation polymer is modified in at least some way, there is no particular limitation on the amount of cyclic ester that is to be melt mixed with the aliphatic condensation polymer.
  • the cyclic ester will generally be used in an amount ranging from about 5 wt.% to about 35 wt.%, preferably 5 wt.% to about 20 wt.%, relative to the mass of the cyclic ester and the aliphatic condensation polymer.
  • the cyclic ester will generally be used in an amount ranging from about 30 wt.% to about 80 wt.%, relative to the total mass of the cyclic ester and the one or more carrier polymers.
  • Cyclic esters used in accordance with the methods of the invention can impart to the resulting modified aliphatic condensation polymers properties such as improved flexibility, an alteration in its hardness (either decreased through the incorporation of softer segments provided by the R group, or increased through crosslinking induced from reaction of functional groups within or pendant from the R group), an alteration in its surface properties (e.g. hydrophobicity provided by the R group), altered degradation rates (either decreased through making the polymer overall more hydrophobic (e.g.
  • hydrophobicity provided by the R group and so less prone to hydrolytic attack, or increased through the introduction via the R group of hydrolytically liable groups to a relatively stable polymer), an alteration in its stiffness (either decreased through the R group breaking up crystallininty, or increased through crosslinking induced from reaction of functional groups within or pendant from the R group), and improved melt viscosity or melt strength resulting directly from the presence of the R group, or through long chain branching induced from reaction of functional groups within or pendant from the R group and the base polymer.
  • an aliphatic condensation polymer may also be converted into a thermoset polymer via reaction of functional groups within or pendant from the R group (e.g. oxidative crosslinking of a coating product produced from the modified polymer, or crosslinking reactions where the modified condensation polymer is included in the formulation of a thermoset resin such as a unsaturated polyester, vinyl ester resin, epoxy resin etc).
  • a thermoset resin such as a unsaturated polyester, vinyl ester resin, epoxy resin etc.
  • the stability (e.g. UV) or colour fastness of a modified aliphatic condensation polymer prepared in accordance with the invention may also be improved by tethering an appropriate moiety to the R group (e.g. moieties such as stabilises (e.g. hindered phenols and hindered amine light stabilisers), alkoxy amines, dyes, and bioactive materials).
  • an appropriate moiety to the R group e.g. moieties such as stabilises (e.g. hindered phenols and hindered amine light stabilisers), alkoxy amines, dyes, and bioactive materials).
  • modified condensation polymers of this invention can advantageously be utilised in products ranging from: films for packaging applications, injection moulded articles, blow moulded containers, sheet products, thermoformed items, coatings, adhesives, fibres, scaffolds for medical applications including tissue repair and drug delivery.
  • Proton NMR spectra were obtained on Bruker AV400 and Bruker AV200 spectrometer, operating at 400 MHz and 200 MHz. All spectra were obtained at 23 0 C unless specified. Chemical shifts are reported in parts per million (ppm) on the ⁇ scale and relative to the chloroform peak at 7.26 ppm ( 1 H) or the TMS peak at 0.00 ppm ( 1 H). Oven dried glassware was used in all reactions carried out under an inert atmosphere (either dry nitrogen or argon). All starting materials and reagents were obtained commercially unless otherwise stated.
  • Removal of solvents "under reduced pressure” refers to the process of bulk solvent removal by rotary evaporation (low vacuum pump) followed by application of high vacuum pump (oil pump) for a minimum of 30 min.
  • Analytical thin layer chromatography (TLC) was performed on plastic-backed Merck Kieselgel KGoOF 254 silica plates and visualised using short wave ultraviolet light, potassium permanganate or phosphomolybdate dip. Flash chromatography was performed using 230-400 mesh Merck Silica Gel 60 following established guidelines under positive pressure. Tetrahydrofuran and dichloromethane were obtained from a solvent dispensing system under an inert atmosphere. All other reagents and solvents were used as purchased.
  • the combined organic layers were washed with saturated aqueous ammonium chloride solution (1 x, 1 A volume of the organic layer), water (1 x, 1 A volume of the organic layer) and brine (1 x, 1 A volume of the organic layer) and dried over sodium sulphate. After filtration, the organic solvent was removed under reduced pressure leaving the crude product. If necessary, the crude product was recrystallised from acetone.
  • the reaction mixture was diluted with water (200 ml), acidified with IN aqueous hydrochloric acid (pH 2) and extracted with diethylether 3 x 100 ml). The combined organic layers were washed with brine (1 x 100 ml) and dried over sodium sulphate. After filtration, the organic solvent was removed under reduced pressure leaving the crude product. The crude product was recrystallised from hexane (4.6 g, 15.4 mmol, 87 %).
  • the reaction mixture was diluted with water (200 ml), acidified with IN aqueous hydrochloric acid (pH 2) and extracted with diethylether 3 x 100 ml). The combined organic layers were washed with brine (1 x 100 ml) and dried over sodium sulphate. After filtration, the organic solvent was removed under reduced pressure leaving the crude product. The crude product was recrystallised from hexane (2.87 g, 14.3 mmol, 81 %).
  • the resulting crude product was dissolved in dry acetone (200 ml), triethylamine (1.36 g, 13.4 mmol) was added and the reaction mixture was heated to reflux for 12 h. After that the solvent was removed under reduced pressure, the crude product was redissolved in diethyl ether (100 ml), successively extracted with 0.5 M aqueous HCl solution (100 ml) and saturated aqueous NaHCO 3 solution and dried over MgSO 4 . The crude product was purified via column chromatography (0.80 g, 2.24 mmol, 67 %).
  • PLA Polylactic acid - Natureworks 305 ID, supplied by Cargill, USA
  • Nylon 11 Rilsan BESNO TL (Check?), supplied by Arkema, France
  • Scheme 2 Schematic setup of the Prism twin screw extruder use to melt modify the polymers with the lactone.
  • the lactone monomer was dried under vacuum at 80C with stirring.
  • the lactone was mixed with 0.1 wt% of the liquid catalyst and then charged into the heated barrel (80C) of an ISCO 500D syringe pump fitted with a heated line to dispense the lactone into the barrel of the twin screw extruder.
  • the gravimetric output of the ISCO syringe pump was calibrated at a number of relevant volumetric throughput rates prior to connecting to the extruder.
  • the polymer was dried in a small scale hopper drier using dry air at temperatures according to the manufacturer's recommendations. All samples were dried to ⁇ lOOppm water, as measured using an Arizona Instruments moisture analyser.
  • the dried polymer was fed to the extruder via a Barrell single screw volumetric feeder.
  • the feeder and extruder hopper were flushed with dry air to prevent moisture ingress.
  • the gravimetric output of the feeder and extruder were monitored by collecting samples before and after collecting samples.
  • the extruder was fitted with a lmm rod die and operated at a throughput of rate of approximately 25g/hour. The exact throughput rate was determined for each sample.
  • the extraded samples which were subsequently melt pressed were collected in sample jars purged with dry nitrogen. Melt pressing was carried in an IHMS melt press ( 250 by 250mm plattern) fitted with brass plates through water could be passed to cool the sample after pressing. Samples were pressed between Teflon sheets. A 150 by 150 by 0.150 mm shim plate was used for the melt pressing.
  • the lactone monomer and catalyst was dissolved in the minimum quantity of solvent (hexane). The solution was coated onto cryo ground polymer powder. The excess solvent was removed by rotovap and vacuum oven.
  • the lactone coated polymer was dried in a small scale hopper drier using dry air at temperatures according to the manufacturer's recommendations. All samples were dried to ⁇ lOOppm water, as measured using an Arizona Instruments moisture analyser.
  • the dried lactone coated polymer was fed to the extruder via a Barrell single screw volumetric feeder.
  • the feeder and extruder hopper were flushed with dry air to prevent moisture ingress.
  • the gravimetric output of the feeder and extruder were monitored by collecting samples before and after collecting samples.
  • the extruder was fitted with a lmm rod die and operated at a throughput of rate of approximately 25g/hour. The exact throughput rate was determined for each sample.
  • the extruded samples which were subsequently melt pressed were collected in sample jars purged with dry nitrogen. Melt pressing was carried in an IHMS melt press ( 250 by 250mm plattern) fitted with brass plates through water could be passed to cool the sample after pressing. Samples were pressed between Teflon sheets. A 150 by 150 by 0.150 mm shim plate was used for the melt pressing.
  • Polymers were dried using the same methodology as was used for the extrusion samples.
  • the lactone samples were vacuum dried prior to use.
  • the 25ml round bottom flasks used for the experiments were cleaned, fitted with large magnetic spinbars and dried in an oven set at 80C. Upon removal from the oven the flasks were stoppered and allowed to cool. Upon opening the flasks to add the reagents, the flasks were flushed with dry nitrogen.
  • the flasks were then placed in a silicone oil bath on top of a magnetic stirrer hotplate.
  • the oil temperature was controlled to the desired temperature (210C for PLA, 240C for Nylon 11) and monitored via a calibrated thermometer.
  • Polymers were dried using the same methodology as was used for the extrusion samples.
  • the lactone samples were vacuum dried prior to use.
  • the 100ml round bottom flasks used for the experiments were cleaned and dried in an oven set at 80C. Upon removal from the oven the flasks were stoppered and allowed to cool. Upon opening the flasks to add the reagents, the flasks were flushed with dry nitrogen. The flasks were then fitted with metal stirrers having two blades. The stirrers were connected to overhead drive motors. The stirrers were held in place by a glass adapter fitted with a Teflon bearing fitted with a rubber seal. The glass adaptor was also fitted with a water cooled Leibig condenser and a separate nitrogen inlet to prevent moisture ingress.
  • the flasks fitted with the adaptors, condensers and stirrers were then placed in a silicone oil bath on top of a magnetic stirrer hotplate.
  • the oil temperature was controlled to the desired temperature ( 200C for PLA, 250C for Nylon 11) and monitored via a calibrated thermometer.
  • stirrers and condensers were removed and samples were poured from the flasks under a blanket of dry nitrogen. The samples were then allowed to cool. For melt pressing samples were reheated in a vacuum oven, sub-samples were removed for analysis from the flasks and were melt pressed using the same procedure as was used for the extrusion samples.
  • Polymer samples were characterised by a number of techniques as described below.
  • the thermal behaviour of the samples was determined by differential scanning calorimetry ( DSC) using a Mettler Toloedo DSC 85 Ie DSC system. Samples were weighed into 40ul pans and lids were crimped onto the pans. A hole was then made in the lids with a 20 gauge needle to prevent pressurisation. All scans were carried out at a scanning rate of 10 degrees Celsius (C) per minute. Scan were typically as follows; (i) heating from 20 to either 180C (polyesters) or 220C (polyamides); (ii) then the pans were held at the elevated temperature for 3 minutes;(iii) then cooled at 10 C/min.
  • a — mole% modifier' calculated as moles of modifier fatty acid.
  • the moles of alpha hydroxyl fatty acid introduced is a multiple of the size of the lactone.
  • For di-lactones 2 moles of acid are introduced per mole of lactone.
  • the modified material can be used as a masterbatch
  • a amount of the modified polymer (Example 15) was dried and was melt mixed with as an equal wt:wt basis with PLA pellets using the method RBF-2.
  • the signal of the hydrogen between carbonyl and alcohol functionality can be used to determine the level of incorporation of symmetric dilactones into the nylon chain. Incorporation of a modifying unit causes a shift in this signal.
  • the signal of the PLA methyl group can be used to determine the level of incorporation of symmetric dilactones into the PLA chain. Incorporation of a modifying unit causes a shift in this signal.
  • # DSC data taken from first heat cycle of sample a - PLA and Nylon 11 controls are for samples which have been melt mixed under the same conditions. Times represent melt mixing times, b - Major peak in bold TENSILE

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un procédé de préparation d'une composition polymère. Ledit procédé consiste à mélanger à l'état fondu un polymère de condensation aliphatique à un ester cyclique qui possède au moins deux fragments ester faisant partie de son cycle, ledit cycle comprenant un fragment α-oxy carbonyle de formule générale (I) dans laquelle R représente un hydrocarbure aliphatique éventuellement substitué possédant au moins 3 atomes de carbone.
PCT/AU2009/000477 2008-04-18 2009-04-17 Polymères de condensation WO2009127009A1 (fr)

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AU2008901955A AU2008901955A0 (en) 2008-04-18 Condensation polymers
AU2008901955 2008-04-18

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US9452143B2 (en) 2012-07-12 2016-09-27 Novus International, Inc. Matrix and layer compositions for protection of bioactives
CN108503531A (zh) * 2018-04-28 2018-09-07 江苏八巨药业有限公司 一种3,3-二甲基-2-氧代丁酸的制备方法
US10584306B2 (en) 2017-08-11 2020-03-10 Board Of Regents Of The University Of Oklahoma Surfactant microemulsions
US10588883B2 (en) 2008-12-09 2020-03-17 Universitat De Les Illes Balears Alpha-derivatives of cis-monounsaturated fatty acids for use as medicines
CN114044886A (zh) * 2021-12-01 2022-02-15 青岛科技大学 一种聚己内酯的生产方法

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Cited By (12)

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Publication number Priority date Publication date Assignee Title
US10588883B2 (en) 2008-12-09 2020-03-17 Universitat De Les Illes Balears Alpha-derivatives of cis-monounsaturated fatty acids for use as medicines
US9011832B2 (en) 2012-02-09 2015-04-21 Novus International, Inc. Heteroatom containing cyclic dimers
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US10457660B2 (en) 2012-02-09 2019-10-29 Novus International, Inc. Heteroatom containing cyclic dimers
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US9655863B2 (en) 2012-07-12 2017-05-23 Novus International, Inc. Matrix and layer compositions for protection of bioactives
US10584306B2 (en) 2017-08-11 2020-03-10 Board Of Regents Of The University Of Oklahoma Surfactant microemulsions
CN108503531A (zh) * 2018-04-28 2018-09-07 江苏八巨药业有限公司 一种3,3-二甲基-2-氧代丁酸的制备方法
CN108503531B (zh) * 2018-04-28 2021-02-26 江苏八巨药业有限公司 一种3,3-二甲基-2-氧代丁酸的制备方法
CN114044886A (zh) * 2021-12-01 2022-02-15 青岛科技大学 一种聚己内酯的生产方法
CN114044886B (zh) * 2021-12-01 2023-08-29 青岛科技大学 一种聚己内酯的生产方法

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